Flat sheet CO2 sorbent

ABSTRACT

A technique for preparing a flat sheet, high capacity CO 2  sorbent and sorbent assembly is disclosed. The sorbent, which is in the form of a sheet, can be a metal oxide/alkali metal carbonate regenerable sorbent, while the sorbent assembly is comprised of the sheet sorbents located between constraining means and gas flow passages.

This is a division of application Ser. No. 07/611,211 filed on Nov. 8,1990, now U.S. Pat. No. 5,454,968.

TECHNICAL FIELD

The present invention relates to a sorbent, and especially to a flatsheet sorbent.

BACKGROUND ART

Maintenance of habitable conditions within closed environments oftenrequires carbon dioxide partial pressures to remain below about 0.5%.Carbon dioxide (CO₂) is conventionally maintained at relatively lowpartial pressures via regenerable and nonregenerable CO₂ sorbents, suchas soda lime, molecular sieves, solid oxide sorbents, and others.

CO₂ sorbents are prepared via paste extrusion or pelletizationtechniques, typically in the form of beads or pellets. Due to chemicaland physical changes associated with absorption/desorption cycles of thesorbent, the life of these sorbents is limited. Cyclical operationscause volume changes in the sorbent which often result in pelletdeterioration and breakage, known as "dusting". As the pelletsdeteriorate, the pressure drop across the sorbent bed increases,resulting in greater power requirements and a less efficient oreffective sorbent bed.

Conventionally, the cyclical life of the solid CO₂ sorbent has beenincreased by the addition of binders or by depositing the activeingredients of the sorbents onto inactive supports, such as porousceramics or carbons. These binders and supports impart strength andprovide high gas/solid contact areas. However, their use is undesirablein applications where the CO₂ loading densities, in addition to weight,volume, and power considerations, are crucial factors. Since the bindersand supports themselves are inactive, "dead" material, they merelyconsume volume and add weight. Therefore, in order to absorb a givenamount of a substance, it is necessary to employ a greater amount ofsupported or bound sorbent than unsupported/unbound sorbent.

What is needed in the art is an unsupported sorbent having high loadingdensities, high CO₂ sorption rates, and extended cyclical life.

DISCLOSURE OF INVENTION

The present invention relates to a CO₂ sheet sorbent for the absorptionof CO₂. The sheet sorbent comprises a mixture of metal carbonate andalkali metal carbonate formed into a flat sheet and constrained by aconstraining means. The sorbent is essentially free of inert material.

This invention also relates to a method for preparing said sheetsorbent. The method comprises preparing a paste-like mixture metalcarbonate and alkali metal carbonate, forming the mixture into a sheet,and constraining the sheet within a constraining means.

The present invention further discloses a sheet sorbent assembly. Thisassembly is comprised of sorbent sheets having sufficient thickness soas to permit sufficient gas permeation rates, means for constrainingsaid sheet sorbents to decrease dusting and inhibit breakage, and ameans for providing gas flow passages which allows contact between thesheet sorbents and a gaseous stream.

Additionally, disclosed is a method for removing CO₂ from a gaseousstream. The gaseous stream is passed through a sorbent sheet assemblyhaving constrained metal oxide/alkali metal carbonate and means forproviding gas flow passages to allow contact between the sorbent sheetsand the gaseous stream. When the gaseous stream contacts the sorbentsheets, the alkali metal carbonate reacts with CO₂ in the gaseous streamto form alkali metal bicarbonate. The metal oxide, in turn, reacts withthe alkali metal bicarbonate to form metal carbonate and regeneratedalkali metal carbonate.

The foregoing and other features and advantages of the present inventionwill become more apparent from the following description andaccompanying drawings.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph of a CO₂ absorption test relating the CO₂ relativeremoval rate to the pH of a solution within a gas/liquid contactor.

FIG. 2 is a cross sectional schematic of the sheet sorbents of thepresent invention constrained by retention screens and stackedalternately with heat exchanger stock fin in a reactor.

BEST MODE FOR CARRYING OUT THE INVENTION

The sorbent of the present invention is a mixture of between about 60 wt% and about 95 wt % metal carbonate and between about 5 wt % and about40 wt % alkali metal carbonate. Between about 70 wt % and about 95 wt %metal carbonate and between about 5 wt % and about 30 wt % alkali metalcarbonate is preferred, while between about 80 wt % and about 92 wt %metal carbonate and between about 8 wt % and about 20 wt % alkali metalcarbonate is especially preferred.

Typically in the form of finely dispersed solid particles, known aspowder, the metal carbonate can be any metal carbonate which isconventionally known in the art and is useful in CO₂ sorption reactions.Some possible metal carbonates include the carbonates of silver, zinc,magnesium, and mixtures thereof, with silver carbonate preferred.

As shown in FIG. 1, an absorption test preformed on an acid/gas system,the relative removal rate of CO₂ (sorption rate) increases as the pH ofthe solution increases. Metal carbonate, such as silver carbonate, isonly moderately alkaline, pH of about 10, while alkali metal carbonateshave pH's above about 12.5. Therefore, to enhance the CO₂ sorptionrates, it is preferred to combine the metal carbonate with alkali metalcarbonate which acts as a sorption promoter. Also typically in the formof powder, the alkali metal carbonates which are useful as sorptionpromoters include: cesium carbonate, potassium carbonate, sodiumcarbonate, and mixtures thereof.

Preparation of the sheet comprises preparing an essentially homogenous,paste or putty like mixture (hereafter referred to as paste-like) of thesorbent powder. The mixture is then formed into a flat sheet. Theformation of the sheet of paste-like mixture is known and conventionaltechniques may be employed in this process. Some conventional techniquesinclude, pressing, molding, and using a roller/die assembly.

For example, the paste-like mixture is formed by preparing an aqueoussolution of alkali metal carbonate. The solution contains sufficientwater such that upon addition of the metal carbonate powder a pliable,paste-like mixture is formed. Metal carbonate powder is then mixed intothe solution to form an essentially homogenous, paste-like mixture.Mixing may be accomplished by any conventional mixing means. Note, ifthe mixture is not homogenous, the sorption efficiency of the sorbentsheet will be decreased. Using a roller die assembly, the paste-likemixture is formed into a flat sheet.

Although the thickness of the sheets is not critical and would be knownto one of ordinary skill in the art, it is preferred that the sheetthickness be optimized to obtain maximum packing density whilemaintaining sufficient mass transfer or gas permeation rates. Masstransfer rates equal to or greater than the desired rate of absorptionare required to maintain constant system gas partial pressures. If themass transfer rate exceeds the rate of absorption the mass transfer zoneis small and sharp break through curves are obtained. Mass transferrates which are less than the rate of absorption require excess sorbentto maintain the desire system partial pressure. The sheet thickness canbe estimated analytically based on a specific application and systemparameters such as required removal rates and maximum partial pressures.

Sheet thickness can be as large as 0.25 inch or larger. For example, fora metal carbonate/alkali metal carbonate sorbent which absorbs betweenabout 0.2 and 0.3 lbs CO₂ /hr, a sheet thickness between about 0.01 andabout 0.25 inches can be used, with a uniform thickness between about0.04 and about 0.125 preferred due to sorption efficiency. If the sheetis too thin, below about 0.01 inches, fabrication of a uniform thicknessbecomes complex, and the number of sheets required to absorb a givenamount of CO₂ increases. On the other hand, if the sorbent sheet is toothick, typically greater than about 0.25 inch, the efficiency of thesorbent decreases due to an inability of CO₂ to diffuse through thethick sheet to be absorbed.

The preferred liquid carrier for the formation of the metalcarbonate/alkali metal carbonate paste-like mixture is water. However,any conventional liquid in which the alkali metal carbonate is inertwith respect to the sorbent constituents and is removable from themixture at a temperature below those which would damage the finalsorbent, can be used. A sufficient amount of liquid is utilized suchthat a paste-like mixture is formed. Excess liquid can cause handlingdifficulty due to low viscosity. Furthermore, if excess liquid isemployed, upon the removal of the liquid (activation or driving off thesorbent), sorbent free areas (voids) can be formed which reduce thepackaging efficiency.

Once the sorbent is formed into a sheet, the sheets are typicallyconstrained to minimize expansion, prevent dusting and breakage, and toprovide structural integrity and ease of handling. The means forconstraining the sheet sorbents can be any means which is not degradedby the sorbent and which allows gas permeation while inhibiting leakageof the sorbent mixture. Possible constraining means include retentionscreens and gas permeable membranes, among others, with fine meshretention screens preferred. The screen mesh should be sufficientlysmaller than the size of metal carbonate or oxide particles and alkalimetal carbonate particles such that particle migration is inhibited.Screens having a mesh of at least 400 have been found suitable for usewith metal oxide/alkali metal carbonate sheet sorbents.

Additionally, Teflon® coating of the screens is useful in preventing theleaching of the sorbent as a soluble salt. The hydrophobiccharacteristics of the Teflon inhibit water from adhering to thescreens, which can cause leaching. As a result, retention screens coatedwith Teflon® are especially preferred.

In a sorbent sheet assembly, the constrained sheet sorbents are stackedwith gas flow passages therebetween. Any means for providing gas flowpassages that separates the sheets, providing cavities which permitgas/sheet sorbent contact, can be used. Suitable means include screens,metallic and nonmetallic foam, heat exchange fin stock, and other rigidporous material.

The sorbent sheet assembly can be used in a sorption process. Thesorbent sheet assembly is loaded into a container for constraining thesorbent sheet assembly and also for forcing a gaseous stream through thesorbent sheet assembly (hereafter referred to as a reactor). Referringto FIG. 2, which is meant to be exemplary not limiting, a reactor isshown which contains a sorbent sheet assembly (50). The sorbent sheetassembly (50) is comprised of sheet sorbents (20), retention screens(30), and heat exchanger fin stock (40). Each sheet sorbent (20) isconstrained between two retention screens (30), and between adjacentconstrained screens (30) are heat exchanger fin stock (40) to allow gasflow and contact between the gas and the sheet sorbents. The sorbentsheet assembly (50) can be held firmly together via pressure or a spacer(60) between the sorbent sheet assembly (50) and one or more of thereactor walls (10).

Prior to use as a sorbent, it may be necessary to heat the sorbent toremove any remaining liquid and to convert the sorbent into a formcapable of sorption, a process known as activation. For example themetal carbonate/alkali metal carbonate sheet sorbents are activated byheating the sorbent, thereby driving off any remaining water andliberating CO₂ by converting the metal carbonate to metal oxide. For asilver carbonate/cesium carbonate sheet sorbent, for example, this isaccomplished by heating the sheet sorbent assembly to between about 160°C. and about 220° C., and then cooling. At these temperatures, thesilver carbonate is converted to silver oxide, releasing CO₂ and water,and converting the constrained paste-like sheets into constrainedporous, dry, solid sheets. Note, temperatures exceeding about 250° C.can irreversibly convert the silver carbonate to silver metal, reducingthe sorbent's CO₂ capacity.

Once activated, a gaseous stream may be introduced to thereactor/sorbent sheet assembly. Sorption for the metal oxide/alkalimetal carbonate sheet sorbent consists of introducing a CO₂ containinggaseous stream to the reactor. Within the reactor, the gaseous streamflows through the cavities provided by the means for providing gas flowpassages. From these cavities the gaseous stream permeates theconstraining means and passes through the sorbent where the C0₂ contactsthe alkali metal carbonate. The alkali metal carbonate, such aspotassium carbonate (K₂ CO₃), and CO₂ react to form alkali metalbicarbonate, such as potassium bicarbonate (KHCO₃) (see reaction 1). Thealkali metal bicarbonate further reacts with the metal oxide, such assilver oxide (AgO), to form metal carbonate, silver carbonate (AgCO₃),and regenerated alkali metal carbonate (see reaction 2). As a result,the alkali metal carbonate is uninhibited from continuing to remove CO₂from the gaseous stream.

    K.sub.2 CO.sub.3 +CO.sub.2 +H.sub.2 O→2KHCO.sub.3   (1)

    2KHCO.sub.3 +AgO→Ag(CO.sub.3)+K.sub.2 CO.sub.3 +H.sub.2 O(2)

Upon conversion of the metal oxide to metal carbonate, the sorbent pHand sorption capabilities decrease, requiring regeneration orreplacement of the sorbent. Regeneration, as with activation, consistsof converting the metal carbonate to metal oxide by heating the sheetsorbents and liberating CO₂. Again, for silver carbonate, temperaturesbetween about 160° C. and about 220° C. are sufficient for CO₂liberation.

Use of the present invention in combination with other sorbents, such ascharcoal, alumina, zeolite molecular sieves, and alkali metal carbonatealone, is anticipated. As with the above described sorbent, thesesorbents would be made into a paste-like consistency via the addition ofwater (or other liquid), formed into a flat sheet of sufficientthickness to allow mass transfer rates approximately equivalent to thedesired rate of sorption, constrained within retention screens, andactivated. Note, activation consist merely of driving off the liquid,and the activation temperatures may differ. Additionally, it may bebeneficial to grind the sorbent to a powder-like consistency beforeaddition of the liquid to increase the active surface area of the finalsheet sorbent.

The following example is given to illustrate the method of preparing thesheet sorbents of the present invention. It is not, however, intended tolimit the generally broad scope of the present invention.

EXAMPLE

The following example describes a method for producing flat sheetsorbents comprised of 12 wt % potassium carbonate and 88 wt % silvercarbonate.

1. An aqueous solution of potassium carbonate was prepared by dispersing12 g of potassium carbonate in 20 ml of water.

2. The potassium carbonate solution was mixed with 88 g of silvercarbonate via an ultrasonic blender for 5 minutes, until homogenous;forming a paste-like mixture.

3. The paste-like mixture was formed into 0.040 inch thick rectangularsheets with a roller/die assembly.

4. 400 mesh Teflon coated stainless steel retention screens where usedto constrain the sorbents.

5. The constrained sorbent sheets were stacked such that 0.020 inch highheat exchanger fin stock was located on each side of the sheets (seeFIG. 2) forming an assembly.

6. The assembly was loaded into a reactor.

7. The sorbent sheets were activated by uniformly heating the reactor to200° C. while purging with air until all of the silver carbonate wasconverted to silver oxide. An infrared analyzer was used to determinewhen the CO₂ concentrations in the effluent air was essentially zero.

At this point, the sorbent can be employed to remove CO₂ from a sorbentstream. Sorbent sheets prepared in the above described manner have shownto have high CO₂ loading densities between about 18 to about 23 lbs/ft³.

The sorbent sheets of the present invention are capable of high CO₂loading densities, and are relatively devoid of the low CO₂ sorptionrates and dusting problems of the prior art. Since the sheets areconstrained, it is not necessary to utilize binders, supports, or otherinert material which tends to decrease the sorbent density. The sheetsorbent of the present invention is essentially free of inert material.

Prior art supported sorbents typically have CO₂ loading densitiesbetween about 2 and 3 lbs/ft³, with dusting problems beginning at about20 cycles (absorption/desorption), while unsupported bound sorbents haveloading densities up to about 15 lbs/ft³ with dusting problems oftenexperienced in early cycles. The sorbent sheets of the present inventionhave shown to possess loading densities above 18 lbs/ft³, typicallybetween about 18 and 23 lbs/ft³ while being devoid of dusting problemsfor more than 100 cycles. Comparative studies using variousmanufacturing techniques for metal oxide/alkali metal carbonate sorbentshas shown the sheet sorbents technique as a marked improvement overother techniques. Additionally, since the sheet sorbent is unsupported,the sorbent assembly consumes minimum volume, making it especiallysuitable for closed environment applications.

Although this invention has been shown and described with respect todetailed embodiments thereof, it will be understood by those skilled inthe art that various changes in form and detail thereof may be madewithout departing from the spirit and scope of the claimed invention.

We claim:
 1. A method for removing CO₂ from a gaseous stream, whichcomprises: passing the gaseous stream through a sheet sorbent assemblyhaving a CO₂ reactive silver oxide/alkali metal carbonate sheet sorbentessentially free of inert materials, constraining means for constrainingsaid sheet sorbent, and means for providing gas flow passages to allowsaid gaseous stream to contact said sheet sorbent as said gaseous streampasses through said sheet sorbent assembly, and flowing said gaseousstream through said means for providing gas flow passages, wherein theCO₂ diffuses into said sheet sorbent, the alkali metal carbonate reactswith the diffused CO₂ to form alkali metal bicarbonate, and the reactivemetal oxide reacts with the formed alkali metal bicarbonate to formmetal carbonate and regenerated alkali metal carbonate.
 2. A method forremoving CO₂ from a gaseous stream as recited in claim 1 wherein saidalkali metal carbonate is selected from the group consisting of cesiumcarbonate, potassium carbonate, sodium carbonate, and mixtures thereof.3. A method for removing CO₂ from a gaseous stream as recited in claim 1wherein said reactive silver oxide/alkali metal carbonate sheet sorbenthas between about 60 wt % and 95 wt % reactive metal oxide and betweenabout 5 wt % and 40 wt % alkali metal carbonate.
 4. A method forremoving CO₂ from a gaseous stream as recited in claim 3 wherein saidreactive silver oxide/alkali metal carbonate sheet sorbent has athickness between about 0.01 inches and about 0.25 inches.
 5. A methodfor removing CO₂ from a gaseous stream as recited in claim 1 furthercomprising heating said formed metal carbonate to desorb CO₂ whereinsaid formed metal carbonate is converted to reactive metal oxide.
 6. Amethod for removing CO₂ from a gaseous stream as recited in claim 5wherein said sheet sorbent is heated to temperatures between about 160°C. and about 220° C. and said sheet sorbent being essentially free ofdusting for greater than 100 regeneration cycles.